Chem 20 Final Review Chemical Bonding Bonding Theory: Valence Electrons & Orbitals • According to bonding theory, valence electrons are classified in terms of orbital occupancy. (0 = empty, 1 = half filled , 2 = full) – An atom with a valence orbital that has a single electron can theoretically share that electron with another atom • Such an electron is called a BONDING ELECTRON – An atom with a full valence orbital (2 e-’s), repels nearby orbitals and wants to be alone • Such a pairing is called a LONE PAIR Covalent Bonding Both atoms have a high EN so neither atom “wins” The simultaneous attraction of two nuclei for a shared pair of bonding electrons = covalent bond Cl2 = diatomic EN difference can be zero = Cl – Cl EN = 3.2 EN = 3.2 EN difference can be small = H - Cl EN = 2.2 EN = 3.2 This is called a polar covalent bond – because one side pulls on the electrons more but we will learn more about this in Section 3.3 Ionic Bonding • The EN of the two atoms are quite different • The atom with the higher EN will remove the bonding e- from the other atom • Electron transfer occurs – Positive and negative ions are formed which electrically attract each other EN = 0.9 EN = 3.2 Metallic Bonding Both atoms have a relatively low EN so atoms share valence electrons, but no actual chemical reaction takes place In metallic bonding: a) e-’s are not held very strongly by their atoms b) the atoms have vacant valence orbitals - This means the electrons are free to move around between the atoms and the (+) nuclei on either side will attract them Analogy: The positive nuclei are held together by a glue of negative e-’s Molecular Elements • Many molecular elements are diatomic and some are polyatomic – You will need to memorize the formulas of the 9 molecular elements as they will not be given to you: Name Symbol hydrogen H2(g) nitrogen N2(g) oxygen O2(g) fluorine F2(g) chlorine Cl2(g) iodine I2(g) bromine Br2(g) phosphorous P4(g) sulfur S8(g) Determining Lewis Formulas • So why do we care about bonding capacity? – If we know how many bonding e-’s an atom has, we can predict what structure a molecular compound willAtom have Number of Number of Bonding capacity valence electrons bonding electrons H carbon 4 4 4 nitrogen 5 3 3 oxygen 6 2 2 halogens 7 1 1 hydrogen 1 1 1 I.e. Carbon can form 4 single bonds, 2 double bonds, 1 triple and 1 single, or 1 double and 2 singles Lewis Formulas – Guided Ex. #2 Determine the Lewis formula & structural formula for the nitrate ion, NO31. Count the valence electrons (*look for a net charge if an ion). nitrogen = 1 x 5 valence e-’s = 5 oxygen = 3 x 6 valence e-’s = 18 23 + 1 (b/c net charge is -1) = 24 2. Which is the central atom? Nitrogen (in lesser quantity) 3. Arrange peripheral atoms around central atom and place 1 pair of valence e-’s between them N Lewis Formulas – Guided Ex. #2 4. Place lone pairs on all peripheral atoms to complete their octet N 5. Place any remaining valence e-’s on the central atom as lone pairs. 6. If the central atom’s octet is not complete, move a lone pair from a peripheral atom to a new position between the peripheral and central atom. 7. If the entity is a polyatomic ion, place square brackets around the entire Lewis formula and then write the net charge outside the bracket on the upper right. N N Pg. 95 Polarity Chemists believe that molecules are made up of charged particles (electrons and nuclei). A polar molecule is one in which the negative (electron) charge is not distributed symmetrically among the atoms making up the molecule. Thus, it will have partial positive and negative charges on opposite sides of the molecule. A molecule with symmetrical electron distribution is a nonpolar molecule. The existence of polar molecules can be demonstrated by running a stream of water past a charged object. Demo: See Figure 9 PREDICTING AND EXPLAINING POLARITY • Pauling explained the polarity of a covalent bond as the difference in electronegativity of the bonded atoms. Cl2(g) – If the bonded atoms have the same electronegativity, they will attract any shared electrons equally and form a nonpolar covalent bond. – If the atoms have different electronegativities, they will form a polar covalent bond. – The greater the electronegativity difference, the more polar the bond will be. • For a very large electronegativity difference, the difference in attraction may transfer one or more electrons resulting in ionic bonding. We use the Greek symbol delta to show partial charges Guided Practice #1 Go to Learning Tip pg. 102 • Predict the polarity of the water molecule. 1) Draw the Lewis formula O 2) VSEPR: Draw the stereochemical formula H H Angular (bent) 3) Assign the EN of the atoms, assign δ– and δ+ to the bonds 4) •Draw in the bond dipoles The bond dipoles (vectors) do not balance. • Instead, they add together to produce a nonzero molecular dipole (shown in red). • This results in a polar molecule (explains bending water) BACKGROUND • There are three types of forces in matter: 1) Intranuclear force (bond) – bonds within the nucleus between protons and neutrons (very strong) 2) Intramolecular force (bond) – bonds between atoms within the molecule or between ions within the crystal lattice (quite strong) 3) Intermolecular force (bond) – bonds between molecules (quite weak); are electrostatic (involve positive and negative charges) There are 3 types of intermolecular bonds: Weakest a) Dipole-Dipole Forces (a.k.a. Polar Forces) Medium b) London Force (a.k.a. London Dispersion Force, Dispersion Force) Strongest c) Hydrogen Bonding Note: “Van der Walls force” – includes London and dipole-dipole forces 1) Dipole-Dipole Force • The simultaneous attraction between oppositely charged ends of polar molecules. ▫ Simply put, the attraction between diploes Dipole: a partial separation of positive and negative charges within a molecule, due to electronegativity differences ▫ Dipole-dipole forces are among the weakest intermolecular forces, but still control important properties (i.e. Solubility because water is polar)) 2) London Force • Simultaneous attraction between a momentary dipole in a molecule and the momentary dipoles in surrounding molecules momentary dipole: an uneven distribution of electrons around a molecule, resulting in a temporary charge difference between its ends They last for just the instant that the electrons are not distributed perfectly even. 3) Hydrogen Bonding • Occurs when a hydrogen atom bonded to a strongly electronegative atom, (N, O and F) is attracted to a lone pair of electrons in an adjacent molecule. ▫ Hydrogen nucleus (proton) is simultaneously attracted to two pairs of electrons; one closer (in the same molecule) and one further away (on the next molecule) Why do you need a strongly electronegative atom? It pulls the hydrogen’s electron away making it “unshielded”, so the lone pair on the other side can come much closer Gases Comparing Kelvin and Celsius Scales • To convert degrees Celsius to Kelvin , you add 273. K = °C + 273 • To convert Kelvin to degrees Celsius, you subtract 273. °C = K - 273 • Examples: – What is 254 K in °C ? -19°C – What is -34°C in K ? 239K Atmospheric Pressure • Pressure exerted by air on all objects Standard Temperature and Pressure (STP) = 101.325 kPa and 0°C • • But laboratory temperatures are not at 0°C So scientists agreed on another set of conditions... Standard Ambient Temperature and Pressure (SATP) = 100 kPa and 25°C • Much closer to lab conditions – so scientists don’t freeze Molar mass • Now you try it… • What is the molar mass of methanol CH3OH? C = 12.01 g/mol x 1 = 12.01 g/mol H = 1.01g/mol x 4 = 4.04 g/mol O = 16.00g/mol x 1 = 16.00 g/mol Molar mass of methanol = 32.05 g/mol Gas Laws • They are based on the temperature, pressure and volume relationships that all gases have in common 1. Boyle’s Law P1V1 = P2V2 2. Charles’ Law V1 = V2 T1 T2 3. Combined Gas Law P1V1 =P2V2 T1 T2 Example: Law of Combining Volumes Use the law of combining volumes to predict the volume of oxygen required for the complete combustion of 120 mL of butane gas from a lighter. 1) The first step is to write the balanced chemical equation, including what you are given and what you need to find: 2C4H10(g) + 13O2(g) → 8CO2(g) + 10H2O(g) 120 mL V=? 2) From this chemical equation you can see that 13 mol of oxygen is required for every 2 mol of butane. Therefore, the volume of oxygen has to be greater than 120mL by a factor of 13/2. VO2: 120 ml C4H10 x ( 13 mL O2) 2 mL C4H10 = 780 mL To make sure that the ratio is used in the correct order, you could include the chemical formula with each quantity as shown above. Note the cancellation of the units and chemical formulas Molar Volume STP = 22.4L/mol SATP = 24.8 L/mol • Molar volume is the same for all gases at the same temperature and pressure (remember, all gases have the same physical properties) – At STP, molar volume = 22.4 L/mol (101.325 kPa and 0°C) – At SATP, molar volume = 24.8 L/mol (100 kPa and 25°C) • This can be used as a conversion factor just like molar mass! At STP, one mole of gas has a volume of 22.4 L, which is approximately the volume of 11 “empty” 2 L pop bottles. Molar Volume – Practice 4. A propane tank for a barbecue contains liquefied propane. IF the tank mass drops by 9.1 kg after a month’s use, what volume of propane gas at SATP was used for cooking? Molar mass (M): C3H8(g) = 44.11 g/mol V C3H8(g) : 9.1 kg x (1 mol ) x ( 24.8 L) = 5.1 kL 44.11g 1 mol What if I wanted your answer in litres? 5.1 kL x 1000L 1 kL = 5100 L = 5.1 x 103 L STP = 22.4L/mol SATP = 24.8 L/mol IDEAL GAS LAW • Before getting too far into this law, it is important to understand the difference between an ideal gas and a real gas.... – IDEAL GAS – does not really exist, it is hypothetical • Follows all gas laws perfectly under all conditions • Does not condense when cooled • Assumes that the particles have no volume and are not attracted to each other – REAL GAS – does not follow gas laws exactly, it deviates at low temperatures and high pressures • Condenses to liquid or sometimes solid when cooled or under pressure • Particles are attracted to each other and have volume • Behaves like an ideal gas at higher temperatures and lower pressures Using the Ideal Gas Law Example One: What mass of neon gas should be introduced into an evacuated 0.88L tube to produce a pressure of 90 kPa at 30°C? PV = nRT n = PV RT n = (90kPa)(0.88L) (8.314 L•kPa/mol•K)(303K) n = 0.0314 mol x 20.18 g = 0.63 g 1 mol Using the Ideal Gas Law – Practice 3. Predict the volume occupied by 0.78 g of hydrogen at 22°C and 125 kPa n H2 = 0.78 g x 1 mol = 0.386 mol 2.02g PV = nRT V = nRT P V = (0.386 mol)(8.314L•kPa/mol•K)(295K) 125 kPa V = 7.573 L V = 7.6 L Solutions Dissociation vs. Ionization • What is the difference between dissociation and ionization? • Both produce (aq) ions... • Dissociation, however, is the separation of ions that already exist before dissolving in water M+X- (s) M+ (aq) + X-(aq) • Ionization involves the production of new ions, specifically hydrogen ions HX0 (aq) H+ (aq) + X-(aq) SUMMARY Substance Process Molecular Disperse as individual, neutral molecules Ionic Dissociate into individual ions Base (ionic hydroxide) Dissociate into positive ions and hydroxide ions Acid Ionize to form hydrogen ions and anions Reference pg. 201 General Equation XY (s/l/g) XY (aq) MX (s) M+ (aq) + X-(aq) MOH (s) M+ (aq) + OH-(aq) HX (s/l/g) H+ (aq) + X-(aq) Bicarbonates: 320 PPM Calcium Ion: 150 PPM Fluoride: 0.12 PPM Magnesium: 4.2 PPM Potassium: 1.2 PPM Sulfates: 43 PPM Sodium: 11 PPM • Amount Concentration (aka Molar Concentration) (mol/L) – the amount of moles of solute per litre of solution; this is the most common form of concentration used in chemistry • c = n solute (mol) Vsolution (L) • Al2(SO4)3 (aq) 2 Al 3+(aq) + 3 SO42- (aq) • c = 0.30 mol/L • [Al 3+(aq)] = 0.30 mol/L x (2) mol/L 1 = 0.60 • [SO42- (aq) ] = 0.30 mol/L x (3) = 0.90 Determining the mass of pure solid for a Standard Solution • Use conversion factors to determine the values for both the amount in moles and the mass of solid required. • Because you are working with one substance, you do not need a balanced equation (No need for a mol ratio) • Volume of the solution and its molar concentration are needed. • Example: To prepare 250.0mL of 0.100 mol/L solution of sodium carbonate, the mass needed is: 0.2500 L x 0.100 mol x 105.99 g = 2.65 g 1L 1 mol Determining the volume of Stock Solution for a Standard Solution • We know that the number of moles does not change when diluting a solution, but the concentration and volume will. So we will use the dilution formula: C1V1 = C2V2 • To use the dilution formula, you must make sure the units are consistent for both the c and v (i.e. both in mL or both in L) • Example: How would you prepare 100 mL of 0.40 mol/L MgSO4(aq) from a solution of 2.0 mol/l MgSO4(aq) C1V1 = C2V2 (2.0mol/L) (V1) = (0.40mol/L) (100mL) V1 = 20 mL Acids and Bases Empirical Definitions Acid – a substance which dissolves in water to produce a solution that: – – – – – Tastes sour Turns blue litmus red Conducts electricity Reacts with active metals to produce H2(g) Neutralizes Bases Base – a substance which dissolves in water to produce a solution that: – – – – Tastes bitter; feels slippery Turns red litmus blue Conducts electricity Neutralizes acids Theoretical Definitions a) Arrhenius: Acid – a substance that forms an acidic solution by dissolving in water to produce free hydrogen ions (H+(aq)) in solution – Example: HCl (aq) H+ (aq) + Cl- (aq) Base – a substance that forms a basic solution by dissolving in water to produce free hydroxide ions (OH-(aq)) in solution – Example: NaOH(aq) Na+(aq) + OH–(aq) Theoretical Definitions b) Modified Definition: Acid – a species that forms an acidic solution by reacting with water to produce hydronium ions (H3O+(aq)) – Example: HCl (aq) + H2O(aq) H3O+(aq) + Cl- (aq) Base – a species that forms a basic solution by reacting with water to produce hydroxide ions (OH-(aq)) – Example: NH3 (aq) + H2O(aq) NH4+(aq) + OH–(aq) The hydronium ion (hydrated proton) – was discovered by Paul Giguère at the Université Laval in 1957. Practice – Naming Acids IUPAC – HClO4(aq) aqueous hydrogen perchlorate – HClO(aq) aqueous hydrogen hypochlorite Traditional – HNO2(aq) nitrous acid – HNO3(aq) nitric acid – H2SO4(aq) aqueous hydrogen sulfate sulfuric acid – H2SO3(aq) aqueous hydrogen sulfite sulfurous acid – H3PO4(aq) aqueous hydrogen phosphate phosphoric acid pH – power of hydrogen [H3O +(aq)] = 10 -pH The pH scale is used to communicate a broad range of hydronium ion concentrations. Most common acids and bases have pH values between 0 and 14 Summary pH = -log [H3O+(aq)] [H3O+(aq)] =10 –pH pOH = -log [OH -(aq)] [OH -(aq)] =10 –pOH • The number of digits following the decimal point in a pH or pOH value is equal to the number of significant digits in the corresponding hydronium or hydroxide concentration. • For both pH and pOH, an inverse relationship exist between the ion concentration and the pH or pOH. The greater the hydronium ion concentration, the lower the pH is. Practice • Pg. 242 #4-7 (pH) • Pg. 243 #9-11 (pOH) Acid – Base Indicators • Other acid-base indicators: – Because the chemical structure of each indicator is different, the pH at which the indicator changes from the HIn(aq) form to the In-(aq) form is different for each indicator. (See inside back cover of textbook) Common name Bromothymol blue Phenolphthalein Color of HIn(aq) pH range of colour change Color of In(aq) Yellow 6.0-7.6 Blue Colourless 8.2-10.0 Pink Practice • Lab Exercise 6.B pg. 247 – Complete the Analysis Portion of the lab below Solution After addition to samples of the solution … A ● ● ● ● methyl violet was blue methyl orange was yellow methyl red was red phenolphthalein was colourless B ● ● ● ● indigo carmine was blue phenol red was yellow bromocresol green was blue methyl red was yellow C ● ● ● ● phenolphthalein was colourless thymol blue was yellow bromocresol green was yellow methyl orange was orange pH range implied by each indicator pH of solution More Practice.... • HI(aq) – explain acidic properties – HI(aq) + H2O(l) H3O+(aq) + I- (aq) • NaCH3COO(aq) – explain basic properties – NaCH3COO(aq) Na+ (aq) + CH3COO-(aq) Simple Dissociation – CH3COO-(aq) + H2O(l) CH3COOH (aq) + OH-(aq) • HOCl(aq) – explain acidic properties – HOCl + H2O(l) H3O+(aq) + OCl- (aq) Try Three More... • H3PO4(aq) – explain acidic properties – H3PO4(aq) + H2O(l) H3O+(aq) + H2PO4- (aq) • Na2SO4 (aq) – explain basic properties – Na2SO4 (aq) 2 Na+ (aq) + SO42-(aq) Simple Dissociation – SO42-(aq) + H2O(l) HSO4- (aq) + OH-(aq) • Sr(OH)2(aq) – explain basic properties – Sr(OH)2(aq) Sr2+(aq) + 2 OH- (aq) Summary • Acids are substances that react with water to produce hydronium ions • Most bases are substances that react with water to produce hydroxide ions • Neutralization can be explained as the reaction between hydronium ions and hydroxide ions to produce water. • Try pg. 253 #4,5 The Difference: Using the Modified Arrhenius Theory • Strong Acids: have high conductivity, high rate of reaction w/ metals and carbonates and a relatively low pH • These empirical properties suggest many ions are present (lots of H3O+ ions present); which is consistent with the idea that strong acids react completely (>99%) with water to form hydronium ions >99% HCl(aq) + H2O(l) H3O+(aq) + Cl-(aq) The Difference: Using the Modified Arrhenius Theory • Weak Acids: have low conductivity, a lower rate of reaction w/ active metals and carbonates and a relatively high pH • These empirical properties suggest fewer hydronium ions are present • Based on this evidence, a weak acid reacts incompletely (<50%) with water to form relatively few hydronium ions <50% CH3COOH(aq) + H2O(l) H3O+(aq) + CH3COO-(aq) Strong and Weak Bases • Strong Bases – all soluble ionic hydroxides that dissociate completely (>99%) to release hydroxide ions NaOH(s) Na+(aq) + OH-(aq) • Weak Bases – an ionic or molecular substance that reacts partially (<50%) with water to produce relatively few hydroxide ions <50% NH3 (aq) + H2O(aq) OH–(aq) + NH4+(aq) Summary Strong Acids Empirical properties (need same concentration & temperature) Modified Arrhenius Theory Weak Acids Strong Bases Weak Bases Very low pH Med to low pH Very high pH Med to high pH High conductivity Low conductivity High conductivity Low conductivity* Fast reaction rate Slow reaction rate Fast reaction rate Slow reaction rate Completely react with water to form H3O+(aq) ions Partially react with water to form H3O+(aq) ions Completely react with water to form OH-(aq) ions Partially react with water to form OH-(aq) ions * Applies only to weak bases that are molecular Polyprotic Acids • With all of these possible reactions you might think that phosphoric acid is very acidic, but only the first reaction is significant. • Also, the first reaction is only 50% complete, so it is actually a weak acid and it has a pH noticeable higher than a strong acid at the same concentration. Acid Concentration pH HCl(aq) 0.1 mol/L 1.0 H3PO4(aq) 0.1 mol/L 1.7 • Based on this evidence: • In general, polyprotic acids are weak acids whose reaction with water decreases with each successive step. NOTE: H2SO4(aq) is a notable exception to this rule. It is a strong acid because it’s first reaction with water is essentially complete. However the second reaction is much less than 50% complete. Stoichiometry What do you remember? In Science 10 you learned about five reaction types, can you match them up Composition (Formation) CH4(g) + O2(g) CO2(g) + H2O(g) Decomposition Mg(s) + O2(g) MgO(s) Combustion Cu(s) + AgNO3(aq) Ag(s) + Cu(NO3)2(g) Single Replacement CaCl2(aq) + Na2CO3(aq) CaCO3(s) + NaCl(aq) Double Replacement H2O(l) O2(g) + H2(g) Using the solubility table: When cancelling spectator ions, they must be identical in every way: chemical amount, form (atom, ion, molecule) and state of matter Practice • Write the net ionic equation for the reaction of aqueous barium chloride and aqueous sodium sulfate. (Refer to the solubility table) • 1) BaCl2(aq) + Na2SO4(aq) BaSO4(s) + 2NaCl(aq) • 2) Ba2+(aq) + 2Cl-(aq) +2Na+(aq) + SO42-(aq) BaSO4(s) + 2Na+(aq) + 2Cl-(aq) (Complete ionic equation) • 3) Ba2+(aq) + 2Cl-(aq) +2Na+(aq) + SO42-(aq) BaSO4(s) + 2Na+(aq) + 2Cl-(aq) • 4) Ba2+(aq)) + SO42-(aq) BaSO4(s) (Net ionic equation) • Ions that are present but do not take part in (change during) a reaction are called spectator ions (like spectators at a sports game: they are present but do not take part in the game) Limiting and Excess Reagents • When no further changes appear to be occurring, we assume that all of the AgNO3(aq) that was initially present has now been completely reacted. • A limiting reagent is the reactant whose entities are completely consumed in a reaction, meaning the reaction stops. – In order to make sure this happens, more of the other reactant must be present than is required • An excess reagent is the reactant whose entities are present in surplus amounts, so that some remain after the reaction ends.. • In our reaction: much more copper was used than needed (evidenced by the unreacted copper) so we assume the reaction ended when no more silver ions were left, so silver nitrate was the limiting reagent. Stoichiometry Calculations (Measured quantity) solids/liquids m n mole ratio solids/liquids m (Required quantity) n Practice #3 (Mass Stoichiometry) What mass of iron (III) oxide is required to produce 100.0 g of iron? Fe2O3(s) + 3 CO(g) m=? M = 159.70g/mol m Fe2O3(s): 100.0 g x 2 Fe(s) + 3 CO2(g) m = 100.0g M = 55.85 g/mol 1 mol x 1 mol x 159.70 g 55.85 g 2 mol 1 mol = 143.0 g Fe2O3 Percent Yield for Reactions • We can use stoichiometry to test experimental designs, technological skills, purity of chemicals, etc. We evaluate these by calculating a percent yield. – This is the ratio of the actual (experimental) quantity of product obtained and the theoretical (predicted) quantity of product obtained from a stoichiometry calculation – Percent yield = actual yield predicted yield x 100 – Some forms of experimental uncertainties: • • • • All measurements (limitations of equipment) Purity of chemical used (80-99.9% purity) Washing a precipitate (some mass is lost through filter paper) Estimation of reaction completion (qualitative judgements i.e. color) Percent Yield Example #1 Example: In a chemical analysis, 3.00 g of silver nitrate in solution was reacted with excess sodium chromate to produced 2.81 g of filtered, dried precipitate. Predicted value: 2AgNO3(aq) + Na2CrO7(aq) Ag2CrO7(s) +2NaNO3(aq) m = 3.00 g M = 169.88g/mol 3.00g x 1 mol x 169.88g 1 mol x 2 mol Percent yield = actual yield predicted yield m= M = 331.74 g/mol 331. 74 g = 2. 93 g 1 mol x 100% = 2.81g x 100% 2.93g = 95.9% Gas Stoichiometry • If 300g of propane burns in a gas barbecue, what volume of oxygen measured at SATP is required for the reaction? • Remember: 24.8L/mol for SATP C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(g) m = 300g 44.11g/mol 300 g x 1 mol 44.11 g V=? 24.8L/mol x 5 mol 1 mol x 24.8 L = 843 L O2(g) 1 mol **Remember – molar volume is the conversion factor for gases just like molar mass is the conversion factor in gravimetric stoichiometry Gas Stoichiometry • What volume of ammonia at 450kPa and 80oC can be obtained from the complete reaction of 7.5kg of hydrogen with nitrogen? 2N2(g) + 3H2(g) 2NH3(g) m = 7500g V=? M = 2.02 g/mol P = 450kPA T = 353.13K 7500 g x 1 mol x 2.02 g PV = nRT V = nRT P 2 = 2475.2475 mol NH3(g) 3 = (2475.2475 mol)(8.314kpa•L/mol•K)(353.15K) (450kPa) = 16150.10L 1.6 x 104 L of NH3(g) Solution Stoichiometry In an experiment, a 10.00 mL sample of sulfuric acid solution reacts completely with 15.9 mL of 0.150 mol/L potassium hydroxide. Calculate the amount concentration of the sulfuric acid. H2SO4(aq) + 2KOH(aq) V = 10.00mL c=? 2H2O(l) + K2SO4(aq) V = 15.9 mL 0.150 mol/L 15.9mL x 0.150 mol x 1mol 1L 2 mol x 1 = 0.119 mol/L 10.0 mL Chemical Analysis Colorimetry Ion Solution colour Group 1, 2, 17 Colourless Cr2+(aq) Blue Cr3+(aq) Green Co2+(aq) Pink Cu+(aq) Green Cu2+(aq) Blue Fe2+(aq) Pale-green Fe3+(aq) Yellow-brown Mn2+(aq) Pale pink Ni2+(aq) Green CrO4 2- (aq) Yellow Cr2O72-(aq) Orange MnO4-(aq) Purple Which solution is which? potassium dichromate sodium chloride sodium chromate potassium permanganate nickel (II) nitrate copper (II) sulfate 6 2 4 1 3 5 1) You want to test the stoichiometric method using the reaction of 2.00 g of copper(II) sulfate in solution with an excess of sodium hydroxide in solution. What would be a reasonable mass of sodium hydroxide to use? To answer this question, you need to calculate the minimum mass required and then add 10%. CuSO4(aq) + 2 NaOH(aq) Cu(OH)2(s) + Na2SO4(aq) 2.00g m=? 159.62g/mol 40.00g/mol 2.00 g x 1 mol x 2 159.62 g 1 x 40.0g 1 mol = 1.00 g 10% = 0.10g 1.00 g x 1.10%= 1.10g Practice pg. 321 #2 2) If 10.0g of copper is placed in solution of 20.0g of silver nitrate, which reagent will be the limiting reagent? All reactants must be converted to moles, then using the mole ratio, determine which reactant will run out first. Cu(s) + 2 AgNO3(aq) 2 Ag(s) + Cu(NO3)2(aq) 10.0g given: 0.157 mol 20.0g 0.0589 mol n Cu(s): 10.0g x 1 mol = 0.157 mol x 2 = 0.315 mol 63.55 g 1 n AgNO3: 20.0g x 1 mol = 0.118 mol x 1 = 0.0589 mol 169.88 g 2 You must test one of the values using the mole ratio. Assume one chemical is completely used up and see if enough of the second chemical is present. That much silver nitrate is not available so copper is not the limiting reagent More copper than that is available so silver nitrate is the limiting reagent Limiting and Excess Reagents Summary • Identify the limiting reagent by choosing either reagent amount, and use the mole ratio to compare the required amount with the amount actually present. • The quantity in excess is the difference between the amount of excess reagent present and the amount required for complete reaction. • A reasonable reagent excess to use to ensure complete reaction is 10%. Chemical Analysis by Titration • Titration – is a common experimental design used to determine the amount concentration of substances in solution. – The solution of known concentration may be either the titrant or the sample; it makes no difference to the analysis • Titration breakdown: – Carefully adding a solution (titrant) from a burette into a measured, fixed volume of another solution (sample) in an Erlenmeyer flask until the reaction is judged to be complete Chemical Analysis by Titration • Burette – precisely marked glass cylinder with a stopcock at one end. Allows precise, accurate measurement and control of the volume of reacting solution. • When doing a titration, there will be a point at which the reaction is complete; when chemically equivalent amounts of reactants have combined. This is called the equivalence point: – Equivalence point – the point during a titration at which the exact theoretical chemical amount of titrant has been added to the sample. (QUANTITATIVE) • To measure this equivalence point experimentally, we look for a sudden change in an observable property, such as color, pH, or conductivity. This is called the endpoint. (QUALITATIVE) Chemical Analysis by Titration • • • • An initial reading of the burette is made before any titrant is added to the sample. Then the titrant is added until the reaction is complete; when a final drop of titrant permanently changes the colour of the sample. The final burette reading is then taken. The difference between the readings is the volume of titrant added. Near the endpoint, continuous gentle swirling of the solution is important Sample Problem • Determine the concentration of hydrochloric acid in a commercial solution. • A 1.59g mass of sodium carbonate, Na2CO3(s), was dissolved to make 100.0mL of solution. Samples (10.00mL) of this standard solution were then taken and titrated with the hydrochloric acid solution. • The titration evidence collected is below. Methyl orange indicator was used. Trial 1 2 3 4 Final burette reading (mL) 13.3 26.0 38.8 13.4 Initial burette reading (mL) 0.2 13.3 26.0 0.6 Volume of HCl(aq) added 13.1 12.7 12.8 12.8 Indicator colour Red Orange Orange Orange TIP: In titration analysis, the first trial is typically done very quickly. It is just for practice, to learn what the endpoint looks like and to learn the approximate volume of titrant needed to get to the endpoint. Greater care is taken with subsequent trials • The initial addition of the titrant (in the burette) to the acid does not produce large changes. This relatively flat region of the pH curve is where a buffering action occurs. • As the titration proceeds, and base is added, some of the acid is reacted with the added base, but anywhere before the equivalence point some excess acid will remain, so the pH stays relatively low. • Very near the equivalence point, a small excess of acid becomes a small excess of base with the addition of a few more drops, so the pH abruptly changes. • The equivalence point is the centre of this change, where the curve is the most vertical. General Rule Strong Acid to Weak Base: pH at equivalence point is always lower than 7 Strong Base to Weak Acid: pH at equivalence point is always higher than 7